DE2517991C3 - Image producing system - Google Patents

Description

- N

-O

- Ν

are, X _{7 is} hydrogen or methyl, X _{8 is} methyl or phenyl and η is 1 or 2.

16. A system according to claim 1, characterized in that the carrier material with 5 to 200 percent by weight, based on the dry weight of the carrier, with the color former solution is impregnated.

17. A system according to claim 1, characterized in that the color formers activated Substance, attapulgite, bentonite, silica, HaI-loysite, kaolin or an acidic or acidic one Clay mineral or a phenolic polymer, a phenol acetylene polymer, a maleic acid-rosin resin or a partially or fully hydrolyzed polymer of maleic anhydride with styrene, ethylene, vinyl ethyl ether or carboxypolymethylene.

18. A system according to claim 1, characterized in that the reactivating substance is an organic acid.

19. A system according to claim 18, characterized in that the organic acid is maleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 1,2,3-propane tricarboxylic acid, diglycolic acid, lactic acid, malic acid, tartaric acid, citric acid, pyrophosphonic acid, benzenesulfonic acid, naphthalene -2-sulfonic acid, 1-phenol-4-sulfonic acid, polymaleic acid ( ₁₀ or copolymers and terpolymers of maleic acid with ethyl acrylate or vinyl acetate, hydroxyalene diphosphonic acid or methylamino-NN-dimethylene phosphonic acid.

20. A system according to claim I. characterized in that the azo coupling components a naphthalene, benzene. Is pyrazolone or quinoline coupling component.

21. A system according to claim 20, characterized in that the azo coupling component a naphthol of the formula

I + CONH

(H)

where M - NH -, - S - or - O -, Z, and Z _{2 are} each hydrogen, nitro, halogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms and m and r are each 1 or 2 are.

22. A system according to claim 20, characterized in that the azo coupling component a naphthylamine of the formula

(12)

where Z ₃ and Z _{4 are} each hydrogen, alkyl with 1 to 4 carbon atoms, benzyl or phenyl and Z ₃ and Z ₄ together with the nitrogen atom to which they are connected form a heterocyclic ring system with 1 or 2 rings, which Contain carbon atoms, nitrogen atoms and at most 1 oxygen atom as ring members, each ring containing 5 to 7 ring members and the ring system having at most 10 ring members and Z _{5 being} hydrogen or a sulfonic acid group.

23. A system according to claim 1, wherein the substrate is neutral or alkaline sized Paper is.

24. System according to claim 1, characterized in that the carrier material is a fabric, Paper. Felt or fabric stamp pad is.

The present invention relates to the production of images with the aid of color formers.

From DT-OS 22 44 610 a pressure-sensitive copying material is known, wherein triazenes as Color formers are used. In this known material, a sheet of paper is on the back with coated with the color former in such a way that it does not become active prematurely, which is achieved by microencapsulation happens. A receiver blue is then combined with an electron acceptor and an azo coupling component coated on the front. If you put the two sheets layer side against layer side brings together and exerts pressure on this 2-sheet system, a copy is made on the recipient sheet the mark on the top sheet.

Deactivators and reactivators will not used.

According to the invention, a carrier material, 7. B. an ink pad with a color former and

Deactivator solution in a high-boiling, weak impregnated with volatile solvents. A substrate, e.g. B. paper, is coated with a solution, which has a color former activator, a reactivator and optionally an azo coupling component contains.

Only through the system according to the invention has it become possible to implement the principle of color formation The development of colorless compounds using electron acceptors can also be applied to paper, soft were previously in use and were therefore exposed to various external influences. Only by the system according to the invention, it is possible on a specific base only by means of a specific Color former to produce a specific colored marking. In known systems, any any recipient blalt, which z. B. with Altapulgus or Silton clay or an acidic phenolic resin has been pretreated by means of any Color former a color effect can be achieved.

The system according to the registration now has the great advantage that it is not compatible with known systems by placing the solution containing the color former and the deactivator on an ordinary, known receiver sheet does not develop any color because it does not contain a reactivator. A well-known one Furthermore, carrier material which only contains the color former and no deactivator does not last long be because the color former by acidic vapors of the environment or by contact with z. B. sour Sweat quickly develops a color and becomes unusable.

In practice, the system according to the invention can e.g. B. look so that the color former together with the deactivator as a solution in an ink pad or typewriter ribbon, while the activator and the reactivator are at a specific point and in a very specific way Form (e.g. pictorially) located on the surface of a paper. When stamping the treated An already existing marking then appears on the surface.

The use of color formers in carbonless materials has long been known, especially in pressure-sensitive carbonless materials. Such systems consist of neighboring leaves, in which by the writing pressure, z. B. by a ballpoint pen or a typewriter copies can be made on the sheet below without using carbon paper, Usually, microcapsules containing a solution of a color former are applied to the back of the top sheet is applied, while the front side is the bottom sheet or the receiver sheet is coated with a Korean substance. In systems that consist of more than two sheets, the sheets in between are coated on both sides with the appropriate substances. When writing or typing on the top sheet of paper, the pressure breaks the capsules, the color former is brought into contact with the reactive substance and a colored image is created, which is a copy of the original.

It is not always necessary to make a copy of the original, and in some cases it is even undesirable. It has now been found that in such cases where only for the original color former are required, it is not necessary to encapsulate the color formers. In the present invention it is also not necessary that the I'arbbildne are colorless, but colored coloring agents can also be used, which are available from Bcriihrci s of the Korean substance a color bottle full draw. Especially so-called azo color formers. wcl before are normally yellow, but their larbi can switch, d. H. in their protonicrlcn grain a different color resulted, have been found for the before

ίο lying invention proved to be advantageous.

Such color formers are very often undesirable in conventional copy painting, since they give the paper a pale yellow color.
The present invention now relates to an image-producing system, which is characterized in that it is a carrier material which is impregnated with a solution of a color former in a slightly volatile, high-boiling solvent and a substance that deactivates the color former, preferably a volatile organic base . and a substrate which, in itself or on at least part of its surface, has a color former activating substance or activating system and a reactivating system and a reactivating substance.

which can counteract the deactivating substance, and wherein the color former contains an azo compound the formula

R ₁

("Xi) ₂ -JH) _n -,
N (1)

CH ₂ I ₂ _ "

is. wherein R ₁ , R ₂ and R _{3 are} each hydrogen, halogen.

₄ c is alkyl, alkoxy. Aryloxy. Alkoxycarbonyl, dialkyl

aminocarbonyl. Acylamino, acyl- (alkyl) -amino or

Y ₁

-SO ₃ -N

are, where Y, and Y _{2 are} each alkyl or aryl or together alkylene, X, hydrogen or alkyl, X ₂ alkyl, cyanoalkyl or arylmethylene or X, and X ₂ together are alkylene, X ₃ alkyl or aryl and η 1 or 2 . Preferably η is 1. On the other hand, the color formers can also have the formula

Z ₁ Z ₂ Z ₃

N = N-N

where Z ₁ , Z ₂ and Z _{3 are} each hydrogen, alkyl, substituted alkyl, alkoxy, halogen, nitro, acylamino, aminoacyl or alkoxycarbonyl, A, and A ₂

809 607/418

each alkyl (Hler phenyl or A ₁ and Λ, together with the nitrogen atom to which they are attached, form a heterocyclic ring and η are I or 2, the substrate then also containing an A / o coupling component.

The invention also relates to a method for producing colored images on a support with the help of color formers. This process is characterized in that a carrier material is used with a solution of a color former in a slightly volatile, high-boiling solvent and one Impregnated color former deactivating substance; that one has a color former activating substance or a system and a reactivating substance, which counteracts the deactivating substance, in the The substrate is incorporated or at least a part of the surface is coated therewith, and the Color former on selected areas of the substrate, which has been prepared as indicated above. transfers, and produces an image, the color former being an azo compound of the general formula Is (1) or (2).

Usually the color former activating substance is a compound which is more acidic than the color former. It can be any compound that acts as a color former activator is known. For example, it can be attapulgite, bentonite, silica, halloysite. Kaolin or any acidic or acidic clay or an acidic polymeric material, such as B. a phenolic polymer, a phenol, I-acetylene polymer, a maleic acid rosin resin or a partially or fully hydrolyzed polymer of maleic anhydride with Styrene. Ethylene, vinyl methyl ether or carboxypolymethylene Act. If the color former is a triazine of the formula (2). so will the color former activating substance usually with an azo coupling component mixed.

The present invention also relates to a solution of a color former of the formula (1) or (2) in one slightly volatile, high-boiling solvent, with a boiling point of at least 150 C and one Color former deactivating substance and a carrier material, which with such a solution is impregnated.

The carrier material with the organic color former solution is impregnated. can e.g. B. be a fabric, e.g. B. a typewriter band, a material from Paper, preferably in tape form, as well as crepe paper, moist or dry ribbed paper or felt or stamp pads, such as those used with rubber or metal stamps, or a felt-tip pen. Preferably the color former is applied to a woven tape to produce a writing machine tape or on a stamp pad made of a felt or a fabric. The color former is then applied to the Transfer the substrate by tapping on the tape or by using the color former with a stamp transfers to the pad with an ink pad. The carrier material can be 5-200% by weight on the dry weight of the carrier, with the solution de .; Color former are impregnated. Preferably 5-100% by weight are used.

As the solvent for the color former arbitrary, low volatile, high boiling solvents into consideration, which has a boiling point of at least 150 ⁰ C, are preferably at least 300 "C

exhibit. Suitable solvents are e.g. B. partially hydrogenated terphenyl. Liquid paraffins, tricresyl phosphate. Di-n-biityl phthalate. Dioctyl phthalate. Trichlorobenzene. Glycerin. Nitrobenzene. Trichloride phosphate or water-insoluble hydrocarbon oils. Alkyl phthaloyl butyl glycolate, such as propyl. Peu-IyI-. Hexyl or, preferably, butyl, phthaloylbulyl glycolates. Diethylene glycol. Triäthylcnglykol or polyethylene glycols with an average molecular weight of 200 W) O. / .. B. 400, or mixtures thereof.

The Faibbildneiiösung can be up to 10 wt .-% Color former included. This depends on the solubility in the chosen solvent. usually amounts of 0.1 to 4% by weight are used.

Suitable, deactivating substances are non volatile, liquid, organic bases, such as amines or alkanolamines, ... B. triethanolamine and diethanolamine.

Suitable reactivating substances are organic Acids that make the maleic. Oxal, malon, amber, Glutar, adipine, 1,2,3-propane tricarbon, diglycol. Milk-. Hydroxy amber, wine, lemon, pyrophosphone, benzenesulfone, naphthalene-2-sulfone, l-phenol-4-sulfonic or polymaleic acid, or Co- and terpolymer of maleic acid with ethyl acrylate and vinyl acetate, hydroxyethane diphosphonic acid. Methylamino-N.N-dimethylene phosphonic acid and similar products. The preferred acid is maleic acid.

The required amount of deactivating substance with which the carrier material must be impregnated. should be so dimensioned that it is produced that the color former when touching the substrate, which does not contain a reactivating substance, is not activated. While in some cases up to 40% by weight deactivating material, based on the solvent, can be used, are sufficient in the Typically up to IO weight percent for most substrates. The amount is preferably 0.4 to 6% by weight. in particular 0.4 to 2% by weight. based on the weight of the solvent.

According to the invention, a paper is preferably used as the substrate, which by means of a neutral or alkaline glue and therefore cannot react with the color former. To the Production of neutral, glued papers is used e.g. B. aluminum sulfate or sodium aluminate or a rosin resin glue, while one is used for the production of alkaline-glued papers Ketene dimers used. With this measure, the color formation reaction can be better controlled.

If azo compounds of the formula (1) are used as color formers, these correspond to prescriptions of the formula (3):

wherein R ^, R ₅ and R _{6 are} each hydrogen, halogen, lower alkyl, lower alkoxy, halogen phenoxy. Phenoxy, low

deralkoxycarbonyl, dialkylaminocarboiiyl, acetylamino, Acetyl-lower alkyl-amino or

- SO, - N

Y ₄

where Y, and Y _{4 are} each lower alkyl or phenyl or together alkylene with 4 or 5 carbon atoms and at most 2 of the radicals R ₄ , R ₅ and R _{h are} hydrogen, X ₄ hydrogen or _{lower alkyl, X 5} lower alkyl. Low cyanoalky! or Benzy! or X ₄ and X ₅ together are alkylene with 4 or 5 carbon atoms, X ,, lower alky! or Pheny! and r. ! or 2.

Of particular importance are azo compounds of the formula (4):

N = N

R ₉

(X ₇ J ₂ -. (- H),.,

(4)

25th

wherein R ₇ , R ₈ and R _{9 are} hydrogen, chlorine. Methyl. Methoxy, phenoxy. Dichlorophenoxy, methoxycarbonyl, dimethylaminocarbonyl, acetylamino. Acetyl- (methyl) -amino or

SO, —N

35

(5)

R ₈

wherein R ₇ , R ₈ , R ₉ , X ₇ and X _{8 have} the meaning given. The color formers of the formula (6) are particularly preferred here:

N = N

(6)

wherein R ₁₀ , R _n and R ₁₂ each represent hydrogen, chlorine, methoxy, methoxycarbonyl, diethylaminosulfonyl or acetylamino, where at most 2 of the radicals R ₁₀ , R ₁₁ and R _{12 are} hydrogen and X ₇ and X _{8 have} the meaning given.

These azo compounds used as color formers are known per se and can be prepared by known methods, / .., by Diazolierung of a corresponding substituted aniline and coupling with a corresponding n-substituicrtcn aniline.

Preferred triazenes of the formula (2) correspond to /. B. the formula

Z ₄ Z ₅ Z ₆

A,

N = N-N

wherein Z ₄ , Z ₅ and Z _{6 are} each hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, halogen, nitro, - N (--X ₁ ) - CO - X, or

- G —N

or - COOX, is, X ₁ and X, each are hydrogen, alkyl with 1 to 4 carbon atoms or phenyl, X is, alkyl with 1 to 4 carbon atoms, G is-CO - or --SO ₂ -, A ₃ , A ₄ , A ₃ and A _{4 are} each alkyl with 1 to 4 carbon atoms or phenyl, or A, and A ₄ or Aj and A ₄ together with the nitrogen atom to which they are connected form a heterocyclic ring system with one or two rings, wherein each ring contains 5 to 7 members and / 7 is 1 or 2. Of very particular interest and therefore very particularly preferred are triazenes of the formula

Z ₆ Z ₇ Z ₈

are, where Y ₅ and Y _{6 are} each methyl. Ethyl or phenyl or together the pentylene group and at most 2 of the radicals R ₇ , R ₈ and R _{9 are} hydrogen, X _{7 is} methyl or ethyl, X _{8 is} methyl, 2-cyanoethyI or benzyl, Xg is methyl or ethyl and η is 1 or 2.

Particularly beneficial results are obtained with color formers of the formula (5):

N = N-N

\ V I

I I n-l

wherein Z ₇ and Z _{8 are} each hydrogen with 1 to 4 carbon atoms. Are alkoxy with I to 4 carbon atoms or halogen and Z ₆ , A ₃ , A ₄ and η have the meaning given.

Particularly favorable results are achieved with color formers of the formula

= N -N

A ₅

obtained in which Z _{9 is} hydrogen, alkyl with 1 or 2 carbon atoms, alkoxy with 1 or 2 carbon atoms, halogen. Nitro or —Nf-X ₄ ) —CO-X ₅ ,

—G — N

or -COOX ₆ , X _{4 is} hydrogen, alkyl having 1 or 2 carbon atoms or phenyl, X _{5 is} alkyl having

1 or 2 carbon atoms, X ₁ , alkyl with I or

2 carbon atoms or phenyl. Z ₁₀ and Z _{11 are} each hydrogen, alkyl with 1 or 2 carbon atoms, alkoxy with 1 or 2 carbon atoms or halogen, (i is -CO --- or -SO ₂ -. A ₅ , A _h . A _s and A ₁ ', each are alkyl with I or 2 carbon atoms or phenyl or A ₅ and A ₁ , or A ₅ and A,', together with the nitrogen atom to which they are connected, a hcterocyelic ring system with I or 2 rings, consisting of Are carbon and nitrogen atoms and at most one oxygen atom as ring members, wol, ei each ring contains 5 to 7 ring members and the ring system has at most H) ring members, and / i is 1 or 2.

Particularly favorable results are obtained with triazene compounds of the formula

(10)

obtained, wherein Z _{12 is} hydrogen, methyl, methoxy, chlorine, nitro,

- N

-N

-SO ₂ -N

-CO-N (CH ₃ I ₂

-COOCH ₃

R _{13 is} hydrogen, methyl, methoxy or chlorine, R _{14 is} hydrogen or methoxy, A ' _{7 is} methyl, ethyl or phenyl, Ag is methyl, ethyl or hydrogen, A _{7 is} methyl, ethyl or phenyl, A _{8 is} methyl or is ethyl or A ₇ and A ₈ together with the nitrogen atom to which they are connected are one of the radicals

- N

are. X- is hydrogen or methyl. X _{H is} methyl or phenyl and ji is 1 or 2.

ι ,, These triazenes are known compounds and can be according to methods known per se will echo. A general manufacturing process can be described as follows, for example: The primary aromatic amine is in hydrochloric acid

is and water dissolved and the solution cooled with ice on O C. Sodium nitrite then gets into the mixture below its surface at such a rate initiated that a small excess of nitrous acid is always present. After completion the diazotization is the reaction mixture to a solution or suspension of the secondary amine and sodium hydrogen carbonate in Water added at! OT. The reaction mixture is stirred and allowed to return to room

2S heat up temperature. Stirring is continued until no more diazonium compounds can be determined. The desired reaction product is precipitated before and is filtered off or extracted using an organic solvent, with water washed and geirocknet in a vacuum at a temperature below 50 C.

The color formers are colorless products and can produce colored images if they are with a typical azo coupling component and an acidic active substrate, i. H. one as a coupling component serving acidic electron acceptor are brought into contact.

When defining the radicals of the color former, lower alkyl or lower alkoxy represent both of the type of the azo compounds, such as those of the triazene compound type, groups 1 to 5, in particular Contain 1 to 4 or 1 to 3 carbon atoms, such as B. amyl, η-butyl, n-butoxy, n-propyl, isopropyl. Ethyl. Ethoxy, methyl or methoxy. Substituted alkyl groups contain suitable substituents z. B. halogen, hydroxy or lower alkoxy.

Halogen in the definitions of the color former is preferably iodine or, in particular, bromine and preferably chlorine.

acyl groups are preferably residues of an aliphatic or aromatic sulfonic or, in particular, carboxylic acid. Residues of alkanecarboxylic acids having 1 to 4 carbon atoms, such as formic, acetic or propionic acid, or residues of a benzene carboxylic acid, such as benzoic acid, are particularly preferred. In the case of acylamino groups, substituents such as lower alkyl can also be used on the amide nitrogen. z. B. methyl have.
Aminoacyl groups are usually amine-substituted — CO — or — SO ₂ groups. The amino group can be the radical of a primary or secondary aliphatic or a heterocyclic amine. If several radicals are together an alkylene group, they together with the nitrogen atom to which they are connected represent a heterocyclic ring such as the piperidine or pyrrolidine ring.
Aryl radicals in the above definitions of

15th

16

Color formers are represented in particular by the naphthalene, diphenyl or, in particular, benzo radicals.

Suitable color formers of the azo type of formula (1) are listed in the following tables. In table

Table 1

is 1 in formula (1) and η is 1 in Table 2 The protonation of the color former was carried out in 95% acetic acid.

No. of substituents in formula (1)

R,

Absorption maximum

'- «ο * (mn)

free base protonated

Color of the protonated dye

- H

2 2-CH, 3 - H 4th - H 5 2-OCH, 6th TJ 7th 2-OCH, 8th 2-OCH, - 9 - H 10 - H 11th IT 12th 2-CH ₃ 13th 2-CH, 14th 2-OCH ₃ 15th 2-OC ₆ H ₅ Cl 16 2-O ^ 17th 2-COOCH, 18th - H

-H

-H

-H

22nd

- H

—H 3-CH,

- H

- H

- H

Ll

- H 3-CI

IJ

3-CI

- H 4-OCH,

- H

- H

- H

3-SO ₂ -I

3-CH,

4-N \

COCH ₃

- H

“J

4-CH ₃

- H 4-OCH ₃ 4-OCH ₃ 5-OCH ₃

- H 4-Cl 4-CH ₃ 4-Cl 5-CI 5-CI 5-CI

- H

- H

4-CH ₃ -CH ₃ -CH,

411

550

violet

3-SO ₂ -N 4-CH,

C ₆ H ₅

4-OCH, CH,

4-N \

COCH ₃

-CH ₃ -CH, -CH, -CH ₃ -CH ₃ -CH ₃ -CH ₃ -CH ₃ -CH, -CH, -CH, -CH, -CH, -CH,

-CH, -CH ₃ -CH, -CH ₃ -CH, -CH ₃ -CH, -CH ₃ -CH, -CH ₃ -CH ₃ -CH ₃ -CH ₃ -CH ₃

- H

4-CO-N

-CH ₃ -CH,

-CH, -CH,

-CH, -CH,

-CH, -CH ₃

-CH, -CH,

-CH ₃ -CH ₃

CH ₃ CH ₃

401 506 orange 406 520 Red 404 528/542 Red 413 540 violet 404 556 violet 412 578 blue-gray 42t 560 Gray 416 510 orange 415 519 orange 413 510 orange 414 506 orange 418 506 orange 420 574 green grey 430 518 orange 418 518 orange 417 518 cherry red 420 514 orange 419 517/535 orange 408 542 Brown 418 520 orange

421

516

orange

-H

-H

4-N

- H 3-CH, \ COCH ₃ - H - H - H 4-CH ₃ 24 2-OCHj -H - H 25th 2-OCH, M. 5-OCH ₃ 26th - H 3-CI - H 27 - H - H 4-Cl 28 -H 3-Cl 4-CH, 29 30th

-CH, -CHjCH ₂ CN

556

violet

CH, -CH ₂ CH ₂ CN 356 522/538 dead CH, -CH ₂ CH ₂ CN 396 534 Brown CH, -CH ₂ CH ₂ CN 400 542 Brown CH ₃ -CH ₂ CH ₂ CN 416 566 Gray CH ₃ -CH ₂ CH ₂ CN 406 513/534 orange CH, -CHjCHjCN 404 523/541 orange CH ₃ CH ₂ CH ₂ CN 404 523/540 orange 809 607/418

17th

18th

continuation

No. Substituents in
R ₁ Formula (l |
R ₂ R., X ₁ X ₂ Absorption color of the
maximum protonized
Dye
/. "" Inml
free base protonated 524/543 brown / orange 31 - H 3-CH ₃ -C ₂ H ₅ -CH ₂ C ₆ H ₅ 400 527/542 Red 32 2-COOCH ₃ - H - H C ₂ H ₅ —CH ₂ C ₁ H ₅ 418 500 orange 33 2-CH ₃ 3-Cl - H -CH ₃ -CH ₃ 413 526 orange 34 2-0-C ₆ H ₅ -H 5-1-C ₅ H ₁₁ -CH ₃ -CH ₃ 416 555 Brown 35 TJ - H 4-OCH ₃ -CH, -CH ₂ CH ₂ CN 398 574 Brown Green 36 2-OCH ₃ 4-OCH ₃ 5-CI -CH ₃ -CH ₂ CH ₂ CN 412 522 violet 37 2-OCH ₃ - H C ₂ H ₅
-5-SO ₂ -N -CH, -CH ₃ 427

C ₃ H ₅

Table!

No. of substituents in formula (1)

R ₁

Absorption maximum

free base

(nm)
protonized

Color of the protonated dye

101 -

102 -H

3-SO ₂ -N

3-SO ₂ -N

CH ₃

CH ₃

4-CH ₃

4-CH ₃

-C ₂ H ₅

-C ₂ H ₅

103 2-CH ₃ - H 4-Cl C ₂ H _5466540

Suitable color formers of the triazole type of the formula (2) are listed in Table 3. Table 3

No. symbols in formula (1)

R ₁

violet

violet

violet

6.1 3-SO ₂ N (CH ₃ ) ₂ 6.2

6.7 3-SO ₂ N (C ₂ Hs) ₂

4-CH ₃

position A ₁ / -Ι A ₂ -N = N .. \ 1 -CH ₃ -CH ₃ -C ₂ H ₅ -C ₂ H ₅

-CH ₃

CH ₃

continuation Symbols in formula (1) C ₆ H ₅ 25 17 991 20th G O O 0 No. R ₁ R ₂ / - \ -CH ₃ -CH ₃ 5 G 19th 3-SO ₂ -N ⁷ y R ₃ π position A ₁ A ₂ / - \ -CH ₃ -CH ₃ 6.11 -N = N ... / - \ > 6.12 \ / / - \ / -Ι 6.13 ] \ I H 1 1 ^^ 0 ^> 6.14 -CH ₃ -CH ₃ / - \ G j 6.15 3-SO ₂ -N ^) / - \ \ / 6.16 6.17 / - \ ] 6.18 6.19 3-SO ₂ -N ^) 4-CH ₃ 6.20 3-SO ₂ -nQ 6.21 6.22 6.23 6.24 6.25 3-SO ₂ -NH-C ₆ H ₅ 6.26 _{/ C} H ₃ 3-SO ₂ -N 6.27 \ 6.28 6.29 6.30 6.31

CH,

6.32 3-SO ₂ -N

continuation Symbols in formula (1) 4-N
\ 4-CO— Ν ' CH ₃ 2-COOCH ₃ 2-SO ₂ -N QH ₅ R ₂ 25 17 991 22nd -CH ₃ -CH ₃ O \ / / 1 No. Ri \
CH ₃ 4-NO ₂ 3-SO ₂ -n'J) G 4-NH-CO-QH ₅ 4-Cl 5-SO ₂ N (C ₂ H ₅ I ₂ C ₂ H ₅ C ₂ H ₅ HIl ^) H 1 -CH ₃ -C ₆ H ₅ 21 3-SO ₂ -N ^) CH ₃ 5-OCH ₃ R ₃ π position A ₁ A ₂ G 6.33 ^< \ / 4-OCH ₃ 4-Cl -N = N ... O 5-OCH ₃ 4-OCH ₃ 6.34 4-SO ₂ N (C ₂ H ₅ ) 5-OCH, H 6.35 4-SO ₂ -N ^) 5-Cl 6.36 C ₂ H ₅ 6.37 CO-CH ₃ H 6.38 2-OCH ₃ 5-Cl 6.39 H H 6.40 H 6.41 2-CH ₃ 6.42 2-OCH ₃ 6.43 6.44 6.45 H 6.46 6.47 6.48 6.49 2-OCH ₃ 6.50 6.51 2-CH ₃ 6.52 2-OCH ₃ 6.53 6.54 2-Cl 6.55 2-CH ₃ 6.56 6.57

continuation

No. symbols in formula (1)

R ₁ R ₂

6.58 4-SO ₂ N (C ₂ H ₅ J ₂
6.59

Position A,

-CH,

-CH ₃

6.60 5-SO ₂ -N (C ₂ H ₅ ),

6.61 - H.

6.62 5-SO ₂ -N (C ₂ Hj) ₂
6.63

6.64 6-SO ₂ -N ">

6.65 5-SO ₂ -N (C ₂ H ₅ I ₂

6.66 5-SO ₂ -N (C ₂ H _{5 I 2}

-C ₂ H ₅

-C ₂ H ₅

-CH ₃

-CH,

When triazenes of the formula (2) are used as a color former of the formula are set, an azo coupling component is also used necessary, which is preferably a naphthalene, benzene, pyrazolone or quinoline derivative or in particular a naphthol or naphthylamine.

Among the naphthols are those of the formula

(12)

OH

/ y,

+ CONH

of particular interest, where M - NH -. - S - or - O-, Z, and Z ₂ each hydrogen. Nitro. Halogen. Are alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms; and m and r are each 1 or 2.

Particularly valuable naphthylamines correspond to where Z ₃ and Z _{4 are} each hydrogen, alkyl with 1 to 4 carbon atoms, benzyl or phenyl and Z ₃ and Z ₄ together with the nitrogen atom to which they are connected form a heterocyclic ring system with 1 or 2 rings , which contain carbon atoms, nitrogen atoms and at most 1 oxygen atom as ring members, each ring containing 5 to 7 ring members and the ring system having at most 10 ring members and Z _{5 is} hydrogen or a sulfonic acid group.

All azo coupling components suitable in the system according to the invention are known couplers used in the production of azo dyes. They are therefore known or can be known as such be produced by known methods. The following naphthols of formula (11) are For example, very suitable as a coupling component:

Table 4

Symbols in formula (6) position of position of -OH —CONH- m

8.1 2 3 1 8.2 2 3 1 8.3 2 3 1 8.4 2 3 1

1 H H 1 4-Cl H 1 4-Cl 2-CH ₃ 1 H 2-OCH,

25th

Fo it set to ng

Symbols in formula (6) position of position of - OH -CONH - 2 3 2 3 2 3 2 3 2 3 2 3 2 3 3 4th 2 3 2 3

H 2-CH ₃ 3-NO ₂ H 5-OCH ₃ 2-OCH ₃ 4-OCHj H 4-OCH ₃ 3-Cl 5-Cl 2-CH ₃ 4-CH ₃ H 4-Cl H 5-OCH., 2-OCH ₃ H H

Suitable naphthylamines of the formula (12) are, for. B.

(9.2)

Other suitable azo coupling components correspond to the following formulas:

(10.7)

COCH ₃

(10.9)

H ₂ C-

-C-CH,

\ (10.1)

COOH

HO OH

OH

HO ₃ S

SO, H

(10.3)

(10.4)

H, N OH

HO ₃ S

SO ₃ H

(10.5)

HO ₃ S

OH

NH-CO-HN

(10.6)

SO ₃ H

A rich palette of colors from orange until violet are produced. Mixtures of such color formers can also be used to create neutral To give shades like gray. A particular advantage of the color formers of the formulas (1) and (2) is that Lightfastness of the colors that are formed from them.

If desired, the color formers of the formulas (1) and (2) can be mixed with one another or the Mixture with other well-known Farbbüdnern such. B. Crystal Violet Lactone (CVL) or Benzoylleucomethylene Blue (BLMB) can be used to achieve certain color changes.

In the following examples, parts and percentages are based on weight.

B e i s ρ i e 1 1

An alkaline sized paper is coated with finely divided clay. A sheet of such paper is overprinted with maleic acid while another sheet is left as such for comparison purposes.

Color former solutions which contain 0.4 of the color former

No. 32 from Table 1, dissolved in diethylene glycol and triethanolamine in various concentrations contain (0.4, 0.8, 1.2, 1.6 and 2%), are used to impregnate a rubber stamp pad. With the help of a rubber stamp, these color former solutions are transferred to the paper.

If the paper that has not been overprinted with maleic acid is stamped, you can use no reaction can be observed in any of the color former solutions. Unless the one printed with maleic acid When paper is stamped, an instant reaction occurs by forming a red color.

27

28

Example 2

Example I is repeated with the exception that
the color former by another color former
is replaced according to the table below. the
used color formers and the resulting colors, provided the paper printed with maleic acid
are stamped in the table below
listed:

Number of the color former
according to table I.

Color of
preserved sculptor

7th
10
14th
15th
17th
18th
21
22nd
23
28
29
32
33
34

Same parts of 7 and 8
Parts 7 and 1 Part 18
Same parts 17 and CVL
Same parts 17 and BLMB

Same parts 17 and 18
and CVL and BLMB

purple
Red

violet

Red-violet

blue

Red

Violet blue

Cherry red

Cherry red

bright red

light red

light red

light red

orange

Orange red

violet

Ocher yellow

Brown

Gray purple

Blue violet

violet

Alternating red

too purple

violet

Example 3

Example 1 is repeated with the exception that
the color former by those of the following
Table is replaced. The substrate is on one side
with a mixture of attapulgus clay with 2.5%
a coupler coated according to Table 4 and then
overprinted with maleic acid. The compounds used and the resulting colors are in the
compiled in the following table:

Color formers

Coupler

No.

Color of the image
Attapulgus tone

6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8

8.7
8.7
8.7
8.7
8.7
8.7
8.7
8.7

Orange red
Orange red
Orange red
Orange red
Orange red
Orange red
Orange red
Orange red

Color former no.

35

6.9 6.10 6.11 6.12

> ° 6.13 6.14 6.15 6.16

6.17 6.18 6.19 6.20

6.23 6.27 6.28 6.29 6.30 6.31 6.32 6.32 6.32

6.32 6.32 6.32 6.32 6.32 6.32 6.40 6.40

6.40 6.40 6.40 6.40

6.40 6.40 6.40 6.40

6.40 6.40 6.40 6.43 6.43 6.44 6.44 6.48 6.49 6.50 6.54 6.54 6.54 6.54 6.54 6.54

55

6o

Coupler

8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 9.1 10.2 10.7 9.2 8.1 8.7 8.5 8.8 8.10 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 8.10 8.11 8.14 10.6 10.2 10.7 10.2 10.7 8.7 8.7 8.7 9.1 10.2 10.7 9.2 8.1 8.7

Color of the image on attapulgus clay

Orange red

Orange red

Orange red

Orange red

Orange red

Orange red

Orange red

Orange red

Orange red

Orange red

Orange red

Orange red

Orange red

Orange red

Orange red

Orange red

Orange red

Orange red

violet

Yellowish red

Bluish red

Red

Red

Yellowish red

Yellowish red

Red

Red

Red

Red

Red

Red

Red

Red

Red

Red

Red

Red

Red

Red

Red

orange

orange

Red

Red

Bluish red

Yellowish red

Red

violet

Yellowish red

Bluish red

Red

Red

Yellowish red

-orlsct / uni!

Color formers

Coupler
No.

Color of the image on attapulgus clay

Color formers

No. %

Coupler

No. %

Color of the image

6.54 8.5 Yellowish red

6.54 8.8 red

6.54 8.10 red b.55 9.1 red

6.55 10.2 violet

6.55 10.7 Bluish purple

6.55 9.2 Reddish gray

6.55 8.1 purple

6.55 8.7 purple

6.55 8.5 Gray violet

6.55 8.8 gray violet

6.55 8.10 Gray violet

6.61 8.7 purple

6.62 8.7 red-violet

6.63 8.7 red-violet

6.64 8.7 red-violet

6.65 8.7 red-violet

6.66 8.7 red-violet

Example 4

Example 3 is repeated except that the following color formers and couplers are used will:

6.65
CVL

1.5
1.5

10.9

2.5

Blue green

Color formers % Coupler % Color of the image No. ' 3 No. 2.25 6.66 8.11 0.25 Red 3 10.1 1.8 6.66 8.11 0.6 orange 3 2.5 6.66 3 10.1 2.5 yellow 6.66 1.5 10.9 2.5 yellow 6.65 8.11 Blue-" 1.5 1.8 Blue violet 6.65 1.5 8.11 0.6 Blue-gray CVL 1.5 10.9 2.5 6.65 1.5 10.1 Blue green CVL

Example 5

ίο example! 1 is repeated with the exception that attapulgus clay is used and that this is incorporated into the mass of the paper so that this has an ash content of 10%. Similar results are thereby obtained.

Example 6

Example 2 is repeated with the exception

that attapulgus clay is used and that this is incorporated into the paper pulp, so that this has an ash content of 10%. Similar results are obtained.

Example 7

Example 1 is repeated, with the exception that instead of diethyl glycol, butyl phthaloyl butyl glycolate is used as a solvent. Similar results are obtained.

Example 8

Example 1 is repeated with the exception that the solvent used is a partially halogenated Terphenyl is used. Similar results are obtained.

Example 9

Ordinary, unfilled paper is coated with the following preparation:

8.0 parts maleic acid,

0.64 parts of sodium carboxymethyl cellulose

of low viscosity,

0.13 part of a methylated methylol melamine. 2.0 parts glycerine,
11.36 parts of water.

The paper coated in this way is stamped with an ink which

0.8 parts of color former no.32 of Table 1,

6.0 parts of diethanolamine.
93.2 parts of diethylene glycol

contains. A strong red color is created immediately.

Claims (15)

Patent claims: 1. An image-producing system, thereby characterized in that it is a carrier material, which with a solution of a color former in a slightly volatile, high-boiling solvent and one that deactivates the color former Substance is impregnated, and a substrate, which in itself or on at least part of its Surface a color former activating substance or an activating system and a reactivating one Substance which can counteract the deactivating substance, and wherein the color former is an azo compound of the formula N = N (D where R ₁ , R ₂ and R _{3 are} each hydrogen, halogen, alkyl, alkoxy, aryloxy, alkoxycarbonyl, dialkylaminocarbonyl, acylamino. Acyl (alkyl) amino or Y ₁ -SO ₂ -N where Y ₁ and Y _{2 are} each alkyl or aryl or together are alkylene, X _{1 is} hydrogen or alkyl, X _{2 is} alkyl, cyanoalkyl or arylmethylene or X ₁ and X _{2 are} together alkylene, X _{3 is} alkyl or aryl and η 1 or 2 or a triazene compound of the formula Z ₁ Z ₂ Z ₃ N = N-N 45 (2) where Z ₁ , Z ₂ and Z _{3 are} each hydrogen, alkyl, substituted alkyl, alkoxy, halogen, nitro, acylamino, aminoacyl or alkoxycarbonyl, A ₁ and A _{2 are} each alkyl or phenyl or A ₁ and A ₂ together with the nitrogen atom , to which they are bound, form a heterocyclic ring and η are 1 or 2 and in the case that the color former is a triazene compound, the substrate also contains an azo coupling component. r, o 2. A system according to claim I, characterized in that the solvent of the color former has a boiling point of at least 150 ° C. 1 A system according to claim 1, characterized in <, <, characterized in that the color former solution contains up to 1 ()% by weight of color former. 4. A system according to claim I, characterized in that the color formers deactivating Substance is a liquid, organic base. 5. A system according to claim 4, characterized in that the base or triethanolamine Diethanolamine is. 6. A system according to claim 1, characterized in that the color former solution up to Contains 40 wt .-% color former deactivating substance. 7. A system according to claim 6, characterized in that the color former solution 0.4 to Contains 6% by weight deactivating substance. 8. A system according to claim 1, characterized in that the color former of the formula N = N [-HJ ₂ -. corresponds to, wherein R _4. , R ₅ and R _{6 are} each hydrogen, halogen. Lower alkyl, lower alkoxy, halophenoxy. Phenoxy, lower alkoxycarbonyl, dialkylaminocarbonyl, acetylamino, acetyl-lower alkyl) -amino or -SO ₂ -N where Y ₃ and Y _{4 are} each lower alkyl or phenyl or together alkylene with 4 or 5 carbon atoms and at most 2 of the radicals R ₄ , R ₅ and R _{6 are} hydrogen, X _{4 is} hydrogen or _{lower alkyl, X 5 is} lower alkyl, lower cyanoalkyl or benzyl or X ₄ and X ₅ together are alkylene having 4 or 5 carbon atoms, X _{6 is} lower alkyl or phenyl and η I or 2. 9. A system according to claim 8, wherein the color former of the formula (X ₇ ) ₂ - "(- H)" -,
N (4) LH ₂ ], -. corresponds to, wherein R ₇ , R ₈ and R _{9 are} hydrogen, chlorine, methyl, methoxy, phenoxy, dichlorophenoxy, methoxycarbonyl, dimethylaminocarbonyl, acetylamino, acetyl- (methyl) -amino or -SO ₂ -N where Y ₅ and Y _{h are} each methyl, ethyl or phenyl or together the pentylene group and at most 2 of the radicals R ₇ , R ₈ and R _{9 are} hydrogen, X _{7 is} methyl or ethyl, X _{8 is} methyl, 2-cyanoethyl or benzyl, X _{9 is} methyl or ethyl and η is 1 or 2. 10. A system according to claim 1, wherein the color former of the formula corresponds to, wherein R ₇ , R ₈ , R ₉ , X ₇ and X _{8 have} the meaning given in claim 9. II. A system according to claim 10, wherein the Color former of the formula corresponds to, wherein R ₁₀ , R ₁₁ and R ₁₂ each represent hydrogen, chlorine, methoxy, methoxycarbonyl, diethylaminosulfonyl or acetylamino, where at most 2 of the radicals R ₁₀ , R ₁₁ and R _{12 are} hydrogen and X ₇ and X _{8 are} those in claim. 9 have given meaning. 12. A system according to claim 1, wherein the Color former of the formula Z ₄ Z ₅ Z ₆ N = N-N (7) corresponds to where Z ₄ , Z ₅ and Z _{6 are} each hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, halogen, nitro, -Ni-X ₁ J-CO-X ₂ or 35 —G — N A ₄ " 40 45 or —COOX ₃ , X ₁ and X _{2 are} each hydrogen, alkyl of 1 to 4 carbon atoms or phenyl, X _{3 is} alkyl of 1 to 4 carbon atoms, G is —CO— or —SO ₂ -, A ₃ , A ₄ , A3 and A _{4 are} each alkyl with 1 to 4 carbon atoms or phenyl, or A ₃ and A ₄ or A ₃ and A ₄ together with the nitrogen atom to which they are connected form a heterocyclic ring system with one or two rings, each ring containing 5 to 7 members and η being 1 or 2. 13. A system according to claim 12, characterized in that the color former of the formula Z ₆ Z ₇ Z ₈ N = N-N (8th) A ₄ corresponds, in which Z ₇ and Z _{8 are} each hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or halogen, and Z ₆ , A ₃ , A ₄ and η have the meaning given in claim 12. 14. A system according to claim 13, wherein the Color former of the formula Z ₉ Z ₁₀ Z ₁₁ N = N-N A ₆ corresponds to, wherein Z _{9 is} hydrogen, alkyl with 1 or 2 carbon atoms, alkoxy with 1 or 2 carbon atoms, halogen, nitro or - N (-X ₄ ) - CO - X ₅ - G-N A ₆ or -COOX ₆ , X _{4 is} hydrogen, alkyl with 1 or 2 carbon atoms or phenyl, X _{5 is} alkyl with 1 or 2 carbon atoms, X _{6 is} alkyl with 1 or 2 carbon atoms or phenyl, Z ₁₀ and Z _{11 are} each hydrogen, Alkyl with 1 or 2 carbon atoms, alkoxy with I or 2 are carbon atoms or halogen, G is —CO— or —SO ₂ -, A ₅ , A ₆ , A ₅ and A _{6 are} each alkyl with 1 or 2 carbon atoms or phenyl, or A ₅ and A ₆ or A ₅ and A ₆ together with the nitrogen atom to which they are connected, a heterocyclic ring system with 1 or 2 rings, consisting of carbon and nitrogen atoms and at most one oxygen atom as ring members, each ring containing 5 to 7 ring members and the ring system having IO ring members, and η is 1 or 2. 15. A system according to claim 13, wherein the Color former of the formula i 2 Z ₁₃ Z ₁₄ corresponds to where Z _{12 is} hydrogen, methyl, methoxy, chlorine, nitro -N (-X ₇ J-CO-X ₈
-SO ₂ -N -SO ₇ -N SO ₂ -N -SO ₂ -O -SO ₂ -N -CO-N (CH ₃ ),
-COOCH ₃ R _{13 is} hydrogen, methyl, methoxy or chlorine, Ri4 is hydrogen or methoxy, A is methyl, ethyl or phenyl, Ag is methyl, ethyl or hydrogen, A _{7 is} methyl. Is ethyl or phenyl, A _{8 is} methyl or ethyl or A ₇ and A ₈ together with the nitrogen atom to which they are connected are one of the radicals